CN102471519B - Method to produce composite material - Google Patents
Method to produce composite material Download PDFInfo
- Publication number
- CN102471519B CN102471519B CN201080030301.9A CN201080030301A CN102471519B CN 102471519 B CN102471519 B CN 102471519B CN 201080030301 A CN201080030301 A CN 201080030301A CN 102471519 B CN102471519 B CN 102471519B
- Authority
- CN
- China
- Prior art keywords
- epoxy
- matrix material
- epoxy resin
- fabric
- epoxy systems
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
- E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
- E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
- E04C5/073—Discrete reinforcing elements, e.g. fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2361—Coating or impregnation improves stiffness of the fabric other than specified as a size
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
Method of producing an elastic composite material comprising the step of impregnating a fiber fabric with a liquid epoxy system comprising a non-aromatic epoxy resin and a hardener, and curing the impregnated fabric, whereby the epoxy system exhibits a tensile modulus lower than 15 MPa after cure.
Description
The present invention relates to produce the method for matrix material.
The second-phase (strengthening material) of matrix material disperses and/or is distributed in first-phase (matrix) and usually used as structured material to use.
The fiber of weather resistance and rigidity can for example be introduced in more soft matrix, to increase intensity and the rigidity of described matrix.This will produce matrix material.Meanwhile, not losing the required mechanical properties of matrix and matrix material conventionally shows and is much higher than the toughness, flexibility and the ductility that are only shown by reinforcing fiber.
Matrix material based on epoxy is for example produced by the fabric with the liquid curable system impregnated carbon, glass, fragrant acid amides or the natural fiber that conventionally comprise epoxy resin and suitable stiffening agent and fabric several minutes to a couple of days of solidifying subsequently dipping under room temperature or comparatively high temps at present.
Prepare the method for this class mixture for example can see in US 4 107 128 or US 6 485 834.
Wherein disperse the curing system of fiber to give matrix material needed mechanical properties, especially acceptable intensity and the elasticity needing, this elasticity can for example be characterized by elastic modulus E.The Young's modulus recording in tension test is called tensile modulus, and the Young's modulus recording in pliability test is called modulus in flexure.Tensile modulus and modulus in flexure are identical in theory for isotropic material.
Typical strengthening material has carbon, glass, fragrant acid amides or natural fiber, and typical curable system for example comprises epoxy resin and suitable stiffening agent, and it constructs and show physical strength and elastic solid matrix after solidifying.
Owing to fiber being introduced in mixture to gain in strength and rigidity, so the selected curable system of matrix material also shows high strength and rigidity conventionally.
Therefore, even if being selected from without any reinforcing fiber in the situation that, the curable system routine of mixture while solidifying, also shows relatively high intensity and rigidity and the curable epoxy system usually above the modulus in flexure of 40MPa.
But, for some application, for example, in automobile and sports industry, not only need high strength, and need high flexibility, high tenacity and soft, to meet all requirements of mechanical part.
Example has body component and the wing (car wing) on race engine.In contest, the parts of being made up of standard mixture on automobile often break and because fragment and fragment may be extremely dangerous.But these parts should withstand this overtaking collision that is inevitably low to moderate moderate energy and shock and can not break.Therefore the material that forms these parts should show excellent shock resistance, wearing and tearing and lancinating, good elongation, tensile strength and high flexibility.
For these application-specific, need:
The security of-improvement;
-better automotive performance (do not need or the less stop off of needs is changed impaired parts, whole schedules maintenance aerodynamic force integrity);
-lower maintenance cost (there is no part replacement).
Cannot mate all these requirements through research and development for the current epoxy systems of conventional composite thing application, especially about the requirement of flexible, toughness and hardness.
Mixture based on many epoxy systems shows high strength and structural texture parts effectively, but shows too high rigidity and modulus in flexure.
In addition, use the conventional epoxy systems of the epoxy resin based on bis-phenol to show all the time inaesthetic yellow or vaporific outward appearance after solidifying, its intensity increases gradually along with being exposed to the time of light.This class material does not have resistivity and unstable for being exposed to uv-radiation.Painted or the vaporific outward appearance of this class can not be accepted in some important application of aesthetic appearance at all.
The problem being solved by the present invention is therefore for producing the matrix material based on epoxy, and it shows excellent impact resistance, high flexibility and quite low modulus in flexure, the good transparency, has resistivity and stability with regard to flavescence and glossiness for uv-radiation.
Described problem solves according to the feature of claim 1.
According to the present invention, solid-state elastic composite is produced by following steps:
With the liquid epoxy systems impregnation of fibers fabric that comprises non-aromatic epoxy resin and stiffening agent, and
Solidify the fabric of dipping, thus the clean epoxy systems that does not have in fiber situation to solidify show lower than 15MPa, preferably lower than 10MPa, more preferably less than the tensile modulus of 5MPa.
Elastic composite is in solid-state material and comprises at least two different phases.Their distortion that demonstrates flexibility in the time standing certain power or stress.Therefore, according to the physical definition of elastic behavior and distortion, this class material is out of shape because applying predetermined power or stress, but returns to its original form and geometrical shape completely in the time removing compelling force or stress.
Because the epoxy systems (matrix) of described mixture shows extremely low tensile modulus, so acquisition has the correspondingly high flexibility mixture of astonishing and unexpected mechanical properties: for structure applications, enough getting well to obtain unusual intensity, but flexibility, elongation and toughness are high surprisingly simultaneously, and tensile modulus is extremely low.Therefore the material of these types can have new application.
Owing to there being prejudice, those skilled in the art is prevented from the combination of fiber and this high flexibility epoxy systems, and this prejudice is this high flexibility epoxy systems because utmost point low modulus and rigidity are not suitable for any structure and machine applications.
Simultaneously, because epoxy resin used according to the invention is non-aromatic epoxy resin, so the material of producing does not show or show few yellow and xanthochromia, therefore, even after light and uv-radiation, it also shows good aesthetic character and transparent color in long-term exposure.The material of producing has resistivity and stable for uv-radiation.
According to a preferred embodiment of the present invention, matrix material according to the present invention show lower than 15GPa, preferably lower than 10GPa, more preferably less than the modulus in flexure of 5GPa.
There is the approach that the material of acceptable intensity and low elastic modulus can be simple and cheap and produce, to make having opened new application as the matrix material based on epoxy.
According to another preferred embodiment of the present invention, at 25 ℃, solidify 1 day, at 40 ℃, the after fixing described epoxy systems of 16 hours has the beginning of the glass transition temperature Tg at the temperature lower than 0 ℃ subsequently.
Because mixture according to the present invention uses conventionally at the temperature higher than 0 ℃, so due to the fact of epoxy systems in rubbery state, this class material will show especially high ductility and low elastic modulus.Traditionally, curing epoxy systems at the temperature lower than Tg for structure applications, to utilize matrix based on the epoxy rigidity in the time of vitreous state.
According to a preferred embodiment of the present invention, epoxy systems purposes for structure applications at the temperature higher than Tg has novelty, and reason is that it makes matrix material show unexpected and surprising toughness and low elastic modulus.
According to another preferred embodiment of the present invention, at 25 ℃, solidify 1 day, at 40 ℃, the after fixing described epoxy systems of 16 hours has the beginning of the glass transition temperature Tg at the temperature lower than-22 ℃ subsequently.Therefore, described epoxy systems until at the temperature of-22 ℃, still remain in rubbery state and described matrix material can be for outdoor utility during winter condition.
According to another preferred embodiment of the present invention, described uncured epoxy systems shows 450mPas or lower viscosity at 25 ℃.The viscosity of described uncured epoxy systems uses the rheometer AR 1500ex buying from TA instruments to use plate, Peltier plate, the circular frequency of 50rpm and the sheet separation of 200 μ m that diameter is 40mm to measure.
Because liquid epoxy systems has utmost point low viscosity, therefore fabric can permeate easily with liquid epoxy systems.Therefore, mixture manufacturing operation is easy to realize, because it does not need expensive professional equipment.In addition, process very simply, make fast parts and cost is effective especially by single shell mould.
According to another preferred embodiment of the present invention, described curing epoxy systems shows the yellowness index lower than 20 expose 200 hours among weather-resistant trier (WOM) the Xenon Ci 5000 buying from Atlas Material Technology after.Under SAE J 1960 test conditionss, accelerate weather-resistant, it describes in United States Patent (USP) 6476158.Test method SAE J 1960 is the weathering resistance for assessment of the parts that use at automobile external by North America automobile industry (the North American Automotive Industry).
Because the epoxy resin for the production of mixture is non-aromatic epoxy resin, therefore the mixture of producing shows the good transparency, brightness and resistance to UV, it is also suitable for having the application of high esthetic requirement.
According to another preferred embodiment of the present invention, described non-aromatic epoxy resin is selected from each molecule and has the aliphatic epoxy resin of at least two epoxy group(ing) or the mixture of at least two kinds of aliphatic epoxy resins that average epoxide functional degree is at least 1.5.
According to another preferred embodiment of the present invention, preferred epoxy resin is diglycidyl ether.
According to another preferred embodiment of the present invention, described fabric comprises carbon, glass, natural fiber, synthon, for example aramid fiber.
Even if use flexibility curable system (matrix), this fibrid also makes to reach needed physical strength, and this matrix shows and is less than the Tg of 0 ℃ and starts.
According to another preferred embodiment of the present invention, described matrix material comprises based on the cumulative volume of mixture and calculates 20-80% volume, preferably 35-65% volume, the more preferably fiber of 40-60% volume.
As too high in the percent by volume of fruit fiber, matrix material enbrittles and shows high rigidity.As too low in the volume fraction of fruit fiber, because epoxy resin-base is very soft, matrix material shows low strength.
The versatility of this high flexibility matrix material makes it be applicable to need final parts to have the Application in manufacture of flexible wide region.Expection is used for needing the novel and non-common mixture field of flexibility, attractive in appearance and security (combine or do not combine).
Preferably be applied as high-performing car and motorcycle industry (racing car, vehicle body, wing), wherein the method according to this invention makes all machinery require to be met.
But, in industry, in any non-structure composite parts or fabricated part, can see chance, such as:
1) fashion and design commodity (for example, necktie, clothes, footwear, watchband, luggage, furniture);
2) boats and ships (for example, carbon sail);
3) physical culture (for example, the body protection facility of footballer's shin bone protector, motorcyclist);
4) shooting (for example, the watch box armor).
Can advantageously introduce the concrete for Structural application according to matrix material of the present invention, to reduce concrete weight and to increase its toughness and elasticity.
Epoxy resin
The epoxy resin using can be monomer, oligopolymer or polymkeric substance, be on the one hand aliphatic, is heterocycle on the other hand.
Example has poly epihydric alcohol base ether and poly-(Beta-methyl glycidyl) ether, and it can be by making the compound that each molecule contains at least two free alcohol radicals react, obtain with alkaline purification subsequently under alkaline condition or under acid catalyst exists with epoxy chloropropane.These ethers can be with gathering (epoxy chloropropane) and acyclic alcohol as ethylene glycol, Diethylene Glycol and senior poly-(ethylene oxide) glycol, the third-1,2-glycol and poly-(propylene oxide) glycol, the third-1,3-glycol, fourth-1,4-glycol, poly-(oxybutylene) glycol, penta-1,5-glycol, oneself-1,6-glycol, oneself-2,4,6-triol, glycerine, 1,1,1-TriMethylolPropane(TMP), tetramethylolmethane and Sorbitol Powder; Cycloaliphatic alcohol is as quinite, two (4-hydroxy-cyclohexyl) methane, 2, prepared by two (4-hydroxy-cyclohexyl) propane of 2-and two (hydroxymethyl) hexamethylene-3-alkene of 1,1-.
Other examples that can mention have poly epihydric alcohol base ester and poly-(Beta-methyl glycidyl) ester, and it can be by making the compound that each molecule contains two or more hydroxy-acid groups react to obtain under alkali exists with epoxy chloropropane, glycerine dichlorohydrine or β methyl epoxy chloropropane.This glycidyl esters of birdsing of the same feather flock together can derive from aliphatic polycarboxylic acid, for example oxalic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid or dimerization or trimerized linoleic acid; Cyclic aliphatic poly carboxylic acid, such as tetrahydrophthalic acid, 4-methyl tetrahydrophthalic anhydride, hexahydrophthalic acid and 4-methylhexahydrophthaacid acid; With poly carboxylic acid as the perhydro aromatic substance of phthalic acid, m-phthalic acid and terephthalic acid.
Particularly preferably based on hydrogenation or perhydro-aromatic substance as the epoxy component of perhydro-dihydroxyphenyl propane or cyclic aliphatic glycidyl epoxy compounds.Hydrogenation or perhydro-aromatic substance refer to the two partially or completely hydrogenation of key of aromatics.Can use the aromatics glycidyl epoxide of other hydrogenations.Also consider the tertiary mixture of above these resins and for example aliphatic many glycidyl epoxies.Wherein, these many glycidyl epoxies are the many glycidyl epoxies derived from short chain or long-chain polyhydric alcohol.
It is also contemplated that containing epoxy compounds those epoxy compounds and purposes for the liquid pre-reaction affixture of the suitable stiffening agent of epoxy resin as mentioned above.Can certainly use the liquid form mixt of the liquid in novel composition.
Below for being applicable to the example of commercially available epoxy product of the present invention: Heloxy
tM48 (trimethylolpropane tris glycidyl ether, by Hexion Specialty Chemicals, Inc. supply); Heloxy
tM107 (diglycidyl ether of cyclohexanedimethanol, by Hexion Specialty Chemicals, Inc. supply); Epalloy
5000 and Epalloy
5001 (epoxidation Hydrogenated Bisphenol A, by CVC Specialties Chemicals, Inc. supply); Hexahydrophthalic acid diglycidyl ester, as Epalloy
5200 (by CVC Specialties Chemicals, Inc. supply) and Araldite
cY 184 (being supplied by Huntsman International LLC); Araldite
dY-N (neopentyl glycol diglycidyl ether is supplied by Huntsman International LLC); Erysis
gE-23 (diglycidyl ether of dipropylene glycol, by CVC Specialties Chemicals, Inc. supply); Polypropylene glycol diglycidyl ether, as Araldite
dY-F (being supplied by Huntsman International LLC) and Erysis
gE-24 (by CVC Specialties Chemicals, Inc. supply); Araldite
dY-L (polypropylene glycol triglycidyl group ether is supplied by Huntsman International LLC); Erysis
gE-35 (the triglycidyl group ether based on Viscotrol C, by CVC Specialties Chemicals, Inc. supply); Triglycidyl group ether based on propoxylated glycerol, as Erysis
gE-36 (by CVC Specialties Chemicals, Inc. supply) and Heloxy
tM84 (by Hexion Specialty Chemicals, Inc. supply); Erysis
gE-120 (based on the diglycidyl ether of dimeracid, by CVC Specialties Chemicals, Inc. supply).
Table 1 represents to be used for implementing three kinds of preferred epoxy resin (Araldite of the present invention
dY-H, Araldite
dY-D, Araldite
dY-C) with for generation of two kinds of epoxy resin (Araldite of comparing embodiment
lY 556, Araldite
dY-T).The viscosity of having pointed out title and having recorded at 20 ℃.
Table 1
Araldite
dY-H, Araldite
dY-D and Araldite
dY-C is the non-aromatic bifunctional epoxy resin with two epoxy group(ing).It is characterized in that viscosity at 20 ℃ is lower than 100mPas.
Araldite
lY 556 is aromatic epoxy resin.
Araldite
dY-T is the non-aromatic trifunctional epoxy resin with three epoxy group(ing).
According to a preferred embodiment of the present invention, described non-aromatic epoxy resin is selected from each molecule and has the aliphatic epoxy resin of at least two epoxy group(ing) or the mixture of at least two kinds of aliphatic epoxy resins that average epoxide functional degree is at least 1.5.
Be less than 1.5 average epoxide functional degree and do not allow enough polyreactions and physical strength.
Stiffening agent
The stiffening agent system using comprises the amine compound that average amine functionality is at least 2.
The amine compound that average amine functionality is at least 2 is preferably selected from alkylene polyamine or polyalkylene polyamine.Preferred example has trimethylhexamethylenediamine, diethylenetriamine, Triethylenetetramine (TETA), tetren, dipropylenetriamine or tri propylidene tetramine; Polyoxyalkylene polyamines or alkylene polyamine, such as polyethyleneoxide diamine and triamine and polypropyleneoxide diamine and triamine; Have and be connected to the amino of ring or the cycloaliphatic diamine of aminoalkyl group or cyclic aliphatic polyamines; By making epoxy resin and thering is at least aliphatic cpd as above, cycloaliphatic compounds or the araliphatic compounds of two or more amino and react the affixture obtaining; There are at least two or more amino N-aminoalkyl piperazines; And polyaminoamide, for example the polyalkylene polyamine of all those polyalkylene polyamines is as mentioned above sour as the reaction product of the polymerization unsaturated fatty acids of trimerized linoleic acid or ricinolic acid with for example polymeric vegetable oil.According to the present invention, can use any mixture of these amine.
Table 2 represents to be used for implementing two kinds of preferred stiffening agent (Aradur of the present invention
53 S and TCD-diamines).Title and the viscosity at 20 ℃ or 25 ℃ are pointed out.All these compounds are all to buy with trade name pointed in table 1 and table 2.TCD-diamines is buied from OXEA GmbH.
Table 2
Epoxy systems (resin adds stiffening agent)
Different rings epoxy resins mixes produce hardenable " epoxy systems " with designated ratio (weight part=pbw) with stiffening agent at 25 ℃.The viscosity of described system is measured at 25 ℃ and 60 ℃.Then, epoxy systems is solidified 1 day at 25 ℃, subsequently after fixing 16 hours at 40 ℃.Subsequently, use Analytical equipment as described below and test conditions to measure glass transition temperature Tg, yellowness index, glossiness, Shore A, Shore D and the tensile property of the cured epoxy system that also physical characterization obtains.
The glass transition temperature Tg of the cured epoxy sample of the 5-15mg in flanging aluminium dish is used in the differential scanning calorimeter Mettler Toledo DSC 822 operating on Windows XP platform and uses immersion cooler Haake EK 90/MT as cooling unit and use nitrogen (20ml/min) to measure as sweeping gas.Temperature scanning with 10K/min from-50 ℃ proceed to+150 ℃.Use at Star
esingle precision type of calibration (calibration type single) (the Mettler-Toledo AG 2008 describing in the 8th part of Software user manual, ME-51710263 G, Switzerland prints 0806/2.12) with the two temperature and the hot-fluid calibration to DSC 822 of indium standard substance and zinc standard substance.The resolving power of Mettler Toledo DSC 822 is 0.04 μ W.Temperature accuracy and precision are 0.2 ℃.
The glass transition temperature Tg of cured epoxy sample (60mm × 10mm × 1mm) is also used according to ISO 6721 the dynamic mechanical analysis instrument DMA type RDS 2 use cooled with liquid nitrogen agent that derive from Rheometric scientific GmbH that operate on Windows XP platform and measures.Temperature scanning with 2K/min from-100 ℃ proceed to+150 ℃.These experiments are carried out with aluminium bending jig.The torque sensitivity of Rheometric scientific GmbH is 2g/cm.Temperature accuracy is 5 ℃ of +/-.
The yellowness index that size is the cured epoxy sample of 120mm × 50mm × 4mm and glossiness at 23 ℃ in sample middle part is being exposed to WOM Xenon Ci 5000 before (0 hour) and exposure under SAE J 1960 test conditionss, measure after 200 hours.As document (Meeten, G.H., Optical Properties of Polymers, Elsevier Applied Science, London, 1986,326-329 page) described in, glossiness is optical property, its interaction based on light and surperficial physical property.Glossiness is actually surface and reflects light to the ability of direction of mirror image.The material with smooth surface seems glossy, and therefore not speculum picture light of very coarse surface seem lackluster.
Yellowness index (YI) is measured and is carried out according to DIN 6167 use Konika Minolta CM-2500 d spectrographs.Glossiness is measured and is used ZEHNTER ZGM 1120 Grossmeters with 60 ° of measured angular to carry out.
The Xiao A hardness of the cured epoxy sample that 10mm is thick and Shore D hardness are measured with FRANK Shore scleroscope at 23 ℃.With hand, sclerometer is being exerted pressure and continued 10 seconds, and recording Shore value.
The stretching that is cured epoxy sample (190mm × 20.5mm × 4mm) according to ISO 527 use Zwick 1474 tensile testing machines at 23 ℃ is measured.The force sensitivity of Zwick 1474 tensile testing machines is that 0.01N and displacement sensitivity are 0.2 μ m.
Table 3a
Table 3a represents to represent the three kinds of epoxy systems (4,5 and 6) for the production of control sample for implementing three kinds of preferred epoxy systems of the present invention (1,2 and 3) and showing 3b.
System 1,2 and 3 discloses for implementing preferred epoxy systems of the present invention, the different aliphatic difunctionals epoxy resin that it comprises different content.The viscosity of liquid uncured epoxy systems 1,2 and 3 at 25 ℃ and 60 ℃ all the time lower than 170mPas.According to DSC method and DMA method, the beginning that the clean epoxy systems 1,2 and 3 solidifying shows the second-order transition temperature at the temperature lower than 0 ℃ all the time.Even if the clean epoxy systems 1,2 and 3 solidifying shows the yellowness index lower than 18 expose 200 hours under SAE J 1960 test conditionss in WOM after all the time.The Shore D hardness of curing epoxy systems 1,2 and 3 is all the time lower than 35.
The tensile modulus of the clean epoxy systems 1,2 and 3 solidifying is all the time lower than 11MPa.
This class character makes epoxy systems 1,2 and 3 be very suitable for producing the high matrix material of flexibility according to the present invention.
The epoxy systems that system 4,5 and 6 discloses for the production of control sample.System 4 comprises trifunctional aliphatic epoxy resin, and system 5 and 6 comprises aromatic epoxy resin.
The viscosity of liquid uncured epoxy systems 4,5 and 6 at 25 ℃ all the time higher than 500mPas.Under this high viscosity, the method for the fiber that is difficult to infiltrate.The second-order transition temperature that curing epoxy systems 5 and 6 shows higher than room temperature.At room temperature, this class system is rigidity.After exposing in WOM 200 hours according to SAE J 1960 test methods, the yellowness index that curing epoxy systems 5 and 6 shows higher than 23.They do not show the good transparency, brightness or resistance to UV and they in time and flavescence.The Shore D hardness of curing epoxy systems 4,5 and 6 is all the time higher than 60.The hardness of these materials is so high so that can not measure Xiao A hardness.
Table 3b
The tensile modulus of curing epoxy systems 4,5 and 6 is higher than 50MPa.Therefore, they show high rigidity and there is no flexibility.Curing epoxy systems 6 crisp its tensile property of immeasurability that makes like this.
These character make epoxy systems 4,5 and 6 be not suitable for producing according to high flexibility matrix material of the present invention.
Produce mixture
Matrix material by with liquid epoxy systems 1 (invention) and liquid epoxy systems 6 (contrast) impregnation of fibers fabric and at 25 ℃, solidify dipping fabric 1 day, at 40 ℃, after fixing is produced for 16 hours subsequently.Or, can make the fabric of dipping at 60 ℃, solidify 2 hours in baking oven.
200g/m
2be of a size of individual layer 2 x 2 twill carbon fabrics (Hexcel 43200) and the 106g/m of 275mm × 110mm
2the 2 layers of plain weave glass fabric (Hexcel 2116) that are of a size of 275mm × 110mm pass through as United States Patent (USP) 5,052 at each experimental session, 906 (SCRIMP
tM) described in the about 130g/m of infuse method
2resin impregnation.Carbon fabric (Hexcel 43200) is carbon 2x2 twill.Each party's each rhizoid bundle upwards intersects with 2 rhizoid bundles on other direction.Described tow is 3000, by 3000 separately diameter be that the high-durability carbon filament of 7 microns forms.The weight of unit surface is 200g/m
2.Glass fabric (Hexcel 2116) is plain weave fabric.Each party's each rhizoid bundle upwards intersects with the rhizoid bundle on other direction.The warp of described tow has 24 threads (with reference to EC7 22) and parallel has 23 threads (with reference to EC7 22).The weight of unit surface is 106g/m
2.
For impregnate fabric, apply vacuum (5 millibars of residual pressures) so that liquid epoxy systems is introduced in fabric.Any direct combination thing working method is all applicable to impregnate fabric, such as wet method spreading, leaching, resin transfer moulding (RTM), filament winding, pressure moulding and pultrusion.(referring to, for example: Daniel Gay, " Materiaux Composites ", Hermes edits, Paris, 1997).
It is feasible that the low viscosity epoxy system using according to the preferred embodiments of the invention is used in this class processing.
In order to compare the flexibility of the mixture of producing, according to following program, impregnate fabric and the curing fabric of carbon fiber (Hexcel 43200) or glass fibre (Hexcel 2116) are carried out to several measurements.
Sample is placed on worktable as shown in FIG. 1 and fixes with weight.
At 23 ℃, measure the amount of deflection H of sample under its deadweight.
In order to calculate modulus (MPa), assumes samples is to be the beam of deflection under its deadweight in constant force.
According to following formula calculating elastic modulus (table 4, the 6th row):
Wherein:
P is the linear weight (table 4, the 2nd row) of sample
L is length (table 4, the 3rd row)
H is amount of deflection (table 4, the 4th row)
I is the inertia modulus of sample:
I＝B×h
3/12
Wherein:
B is the width (110mm) of sample
H is thickness (table 4, the 5th row).
The fiber volume fraction of composite sample according to calculating with following formula (referring to, for example: Daniel Gay, " Materiaux Composites ", Hermes edit, Paris, 1997, the 59th page of reference):
Wherein:
N
pfor the number of plies (number of plies)
M
offor the weight (table 4, the 7th row) of fabric unit surface
ρ
ffor fibre density (table 4, the 8th row)
V
ffor fiber volume fraction (table 4, the 9th row)
H is the thickness (table 4, the 5th row) of sample
The results are summarized in table 4 of measurements and calculations.
Table 4
Table 4 proves, compared with the matrix material that uses epoxy systems 6 to produce, the matrix material of using epoxy systems 1 according to the present invention to produce shows much higher amount of deflection H (> 140mm) and much lower elastic modulus E (< 6.5GPa).
By the method according to this invention, in matrix material, can obtain high surprisingly amount of deflection and low Young's modulus unexpectedly.This class mixture can be used for needing intensity and both new application of flexibility simultaneously.
Claims (1)
1. the method for producing elastic composite, it comprises the following steps:
A) with the liquid epoxy systems impregnation of fibers fabric that comprises non-aromatic epoxy resin and cycloaliphatic diamine stiffening agent, described cycloaliphatic diamine has the amino or the aminoalkyl group that are connected to ring; With
B) solidify the fabric flooding, it is characterized in that described epoxy systems shows the tensile modulus lower than 15MPa when curing, and show the beginning of the glass transition temperature Tg at the temperature lower than 0 ℃,
And described elastic composite comprises the fiber based on described total composite volume calculating 20%-80% volume and shows the modulus in flexure lower than 15GPa.
2. the process of claim 1 wherein that described epoxy systems shows the viscosity lower than 450mPas at 25 ℃.
3. the method for claim 1 or 2, wherein said epoxy systems shows the yellowness index lower than 20 after exposing 200 hours according to SAE J 1960 test conditionss in weather-resistant trier WOM Xenon Ci 5000.
4. the method for claim 1 or 2, wherein said non-aromatic epoxy resin is that each molecule has the aliphatic epoxy resin of at least two epoxy group(ing) or the mixture of at least two kinds of aliphatic epoxy resins that average epoxide functional degree is at least 1.5.
5. the method for claim 4, wherein said non-aromatic epoxy resin is diglycidyl ether.
6. the method for claim 1 or 2, wherein said fabric comprises carbon, glass, fragrant acid amides or natural fiber.
7. the matrix material obtaining by the method for any one in aforementioned claim.
8. the matrix material of claim 7, it comprises the fiber that calculates 30%-70% volume fraction based on described total composite volume.
9. the parts of automobile or racing car, its matrix material by claim 7 or 8 is made.
10. concrete, the matrix material that it comprises claim 7 or 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09164005 | 2009-06-29 | ||
| EP09164005.2 | 2009-06-29 | ||
| PCT/EP2010/057529 WO2011000646A1 (en) | 2009-06-29 | 2010-05-31 | Method to produce a composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102471519A CN102471519A (en) | 2012-05-23 |
| CN102471519B true CN102471519B (en) | 2014-05-14 |
Family
ID=41059023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080030301.9A Expired - Fee Related CN102471519B (en) | 2009-06-29 | 2010-05-31 | Method to produce composite material |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US9034776B2 (en) |
| EP (2) | EP2465894A1 (en) |
| JP (1) | JP5528549B2 (en) |
| KR (1) | KR20120047854A (en) |
| CN (1) | CN102471519B (en) |
| AU (1) | AU2010268300A1 (en) |
| TW (1) | TWI527952B (en) |
| WO (1) | WO2011000646A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8802792B2 (en) * | 2010-09-17 | 2014-08-12 | Empire Technology Development Llc | Partially hydrogenated bisphenol-A-based polymers as substitutes for bisphenol-A-based polymers |
| RU2461588C1 (en) * | 2011-04-01 | 2012-09-20 | Общество с ограниченной ответственностью Научно-производственная фирма "УралСпецАрматура" | Composite reinforcing article |
| WO2013100212A1 (en) * | 2011-12-27 | 2013-07-04 | 코오롱인더스트리(주) | Method for manufacturing an aramid composite |
| RU2509653C1 (en) * | 2012-08-27 | 2014-03-20 | Общество с ограниченной ответственностью Научно-производственная фирма "УралСпецАрматура" | Composite reinforcements |
| EP2978883B1 (en) * | 2013-03-25 | 2018-02-14 | DSM IP Assets B.V. | Clothing comprising a fabric, comprising elastic fibers |
| WO2015094308A1 (en) * | 2013-12-19 | 2015-06-25 | Carbitex, LLC | Flexible fiber-reinforced composite material |
| US9370904B2 (en) | 2013-12-19 | 2016-06-21 | Carbitex, LLC | Flexible fiber-reinforced composite material |
| EP3091135A1 (en) * | 2015-05-04 | 2016-11-09 | Evonik Degussa GmbH | Reinforcing rod, method for production and use |
| LT3260436T (en) * | 2016-06-23 | 2020-02-25 | Evonik Operations Gmbh | Reinforced building block made of autoclaved aerated concrete (aac) |
| US10959344B2 (en) | 2017-10-06 | 2021-03-23 | Trench Limited | Outdoor electrical apparatus having an outer housing arranged to selectively encase a main encapsulant |
| RU2699249C2 (en) * | 2017-10-18 | 2019-09-04 | Общество с ограниченной ответственностью "АЛИТ-ТМ" | Method for production of reinforced articles from autoclave foam concrete and article |
| JP7487865B2 (en) * | 2020-02-27 | 2024-05-21 | 国立大学法人東海国立大学機構 | Hose, hose manufacturing method, and hydraulic pump |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127508A (en) * | 1995-11-16 | 2000-10-03 | Shell Oil Company | Epoxy resin and amine-terminated polyamide from aminoalkylpiperazine |
| CN1578799A (en) * | 2001-11-07 | 2005-02-09 | 东丽株式会社 | Epoxy resin compositions for fiber-reinforced composite materials, process for production of the materials and fiber-reinforced composite materials |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3441522A (en) * | 1965-08-16 | 1969-04-29 | Union Carbide Corp | Curable,tacky polymers of water and a polyepoxide and process for the preparation thereof |
| US3934067A (en) * | 1974-07-17 | 1976-01-20 | Western Electric Company, Inc. | Laminar structure having an impregnated fibrous web |
| US4107128A (en) | 1975-02-20 | 1978-08-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Carbon fiber composition |
| US4746718A (en) * | 1987-04-06 | 1988-05-24 | Amoco Corporation | Novel oligomeric diamine hardeners and their use for curing epoxy resin systems |
| US5052906A (en) | 1989-03-30 | 1991-10-01 | Seemann Composite Systems, Inc. | Plastic transfer molding apparatus for the production of fiber reinforced plastic structures |
| US5681014A (en) * | 1992-05-15 | 1997-10-28 | Palmer; Harry W. | Torsional twist airfoil control means |
| DE4342722A1 (en) * | 1993-12-15 | 1995-06-22 | Hoechst Ag | Elastic epoxy resin hardener system |
| FR2753978B1 (en) | 1996-09-30 | 1999-05-14 | Inst Francais Du Petrole | THERMOSETTING COMPOSITION, USES THEREOF AND FOLDABLE FLEXIBLE PREFORM COMPRISING THE SAME |
| US6476158B1 (en) | 1999-08-31 | 2002-11-05 | General Electric Company | Process for colored polycarbonate-polyester compositions with improved weathering |
| JP2003055011A (en) * | 2001-08-09 | 2003-02-26 | Aisawa Construction Co Ltd | Rod for reinforcing concrete and manufacturing method therefor |
| AU2003244466A1 (en) * | 2002-02-06 | 2003-09-02 | Sekisui Chemical Co., Ltd. | Resin composition |
| US20120142816A1 (en) * | 2006-11-20 | 2012-06-07 | Dow Global Technologies Inc | Novel epoxy hardeners with improved cure and polymers with enhanced coating properties |
-
2010
- 2010-05-31 AU AU2010268300A patent/AU2010268300A1/en not_active Abandoned
- 2010-05-31 US US13/381,106 patent/US9034776B2/en not_active Expired - Fee Related
- 2010-05-31 EP EP20120156621 patent/EP2465894A1/en not_active Withdrawn
- 2010-05-31 CN CN201080030301.9A patent/CN102471519B/en not_active Expired - Fee Related
- 2010-05-31 EP EP20100724424 patent/EP2449013A1/en not_active Withdrawn
- 2010-05-31 WO PCT/EP2010/057529 patent/WO2011000646A1/en active Application Filing
- 2010-05-31 JP JP2012516613A patent/JP5528549B2/en not_active Expired - Fee Related
- 2010-05-31 KR KR20117030197A patent/KR20120047854A/en not_active Application Discontinuation
- 2010-06-28 TW TW099121006A patent/TWI527952B/en not_active IP Right Cessation
-
2012
- 2012-02-17 US US13/399,053 patent/US20120149266A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127508A (en) * | 1995-11-16 | 2000-10-03 | Shell Oil Company | Epoxy resin and amine-terminated polyamide from aminoalkylpiperazine |
| CN1578799A (en) * | 2001-11-07 | 2005-02-09 | 东丽株式会社 | Epoxy resin compositions for fiber-reinforced composite materials, process for production of the materials and fiber-reinforced composite materials |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2465894A1 (en) | 2012-06-20 |
| EP2449013A1 (en) | 2012-05-09 |
| WO2011000646A1 (en) | 2011-01-06 |
| US20120149266A1 (en) | 2012-06-14 |
| KR20120047854A (en) | 2012-05-14 |
| TW201105835A (en) | 2011-02-16 |
| JP2012531481A (en) | 2012-12-10 |
| CN102471519A (en) | 2012-05-23 |
| US20120122360A1 (en) | 2012-05-17 |
| TWI527952B (en) | 2016-04-01 |
| US9034776B2 (en) | 2015-05-19 |
| AU2010268300A1 (en) | 2012-01-19 |
| JP5528549B2 (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102471519B (en) | Method to produce composite material | |
| CN104395381B (en) | Fiber reinforced composite material | |
| JP6497370B2 (en) | Epoxy resin composition, and film, prepreg and fiber reinforced plastic using the same | |
| CN107011628A (en) | For the composition epoxy resin for the composite for preparing stable storing | |
| JP6766888B2 (en) | Thermosetting resin compositions, prepregs, and fiber-reinforced composite materials and methods for producing them. | |
| CN104918987A (en) | Epoxy resin composition, prepreg, fiber reinforced plastic material, and manufacturing method for fiber reinforced plastic material | |
| KR102294515B1 (en) | Epoxy Resin Compositions, Prepregs and Fiber Reinforced Composites | |
| CN104583265A (en) | Epoxy resin composition and film, prepreg, and fiber-reinforced plastic using same | |
| WO2014030636A1 (en) | Epoxy resin composition and film, prepreg, and fiber-reinforced plastic using same | |
| CN107250197B (en) | Composition epoxy resin, prepreg and fibre reinforced composites | |
| DE1720427B2 (en) | Thermosetting epoxy resin mixtures | |
| EP3613788A1 (en) | Epoxy resin composition, prepreg, and carbon fiber-reinforced composite material | |
| WO2013113587A1 (en) | Hyperbranched polymers for modifying the toughness of hardened epoxy resin systems | |
| WO2019026724A1 (en) | Sheet molding compound, prepreg, and fiber-reinforced composite material | |
| ES2920330T3 (en) | Epoxy resin composition, molding material for fiber reinforced composite material and fiber reinforced composite material | |
| JPWO2018216643A1 (en) | Epoxy resin composition for fiber reinforced composite material, and fiber reinforced composite material | |
| Alsagayar et al. | Mechanical properties of epoxidized palm oil/epoxy resin blend | |
| US20210253808A1 (en) | Heat-curable molding material, fiber-reinforced composite, heat-curable epoxy resin composition for fiber-reinforced plastic, production method for heat-curable molding material, and fiber-reinforced plastic | |
| JP6163763B2 (en) | Epoxy resin composition, prepreg and film using the same, and fiber reinforced composite material | |
| KR20180083662A (en) | Modified epoxy resin, preparation method thereof and thermosetting resin composition comprising the same | |
| JP7264237B2 (en) | Epoxy resin composition, prepreg, and fiber reinforced composite | |
| JP2024021045A (en) | Prepreg, fiber-reinforced composite material, tubular body made from fiber-reinforced composite material, golf club shaft, and fishing rod | |
| CN112638983A (en) | Improvements in or relating to curing agents | |
| EP0482483A2 (en) | Heat sealing of textiles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140514 Termination date: 20150531 |
|
| EXPY | Termination of patent right or utility model |